CN103270099B - Molded thermoplastic articles comprising thermally conductive polymers - Google Patents
Molded thermoplastic articles comprising thermally conductive polymers Download PDFInfo
- Publication number
- CN103270099B CN103270099B CN201180061463.3A CN201180061463A CN103270099B CN 103270099 B CN103270099 B CN 103270099B CN 201180061463 A CN201180061463 A CN 201180061463A CN 103270099 B CN103270099 B CN 103270099B
- Authority
- CN
- China
- Prior art keywords
- weight
- thermoplastic
- product according
- acid
- molded thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed are molded thermally conductive thermoplastic articles having low light reflectance, comprising thermoplastic polymers blended with thermally conductive fillers and carbon black powders. The polymer blends are characterized by a unique combination of high thermal conductiveness and low light reflectance. The molded articles in which such properties are desirable include, without limitation, a chassis structure for electrical and electronic devices wherein a light source is constructed inside and wherein heat is generated in the light source so as to be dissipated to an ambient atmosphere.
Description
Technical field
The present invention relates to molding heat conduction thermoplastic article, described molding heat conduction thermoplastic article has light reflectivity, and comprises and heat conductive filler and the blended thermoplastic polymer of carbon black powder.The feature of blend polymer is the unique combination of high thermal conductivity and light reflectivity.More specifically, the present invention relates to the moulded parts with this type of performance, described moulded parts unrestrictedly comprises the understructure for Electrical and Electronic device, and wherein light source is in internal build, and wherein heat produces so that heat is dispersed in ambient air from light source.
Background technology
Many Electrical and Electronic devices comprise luminous package in the structure, such as mold frame, understructure or metal bottom cover.These can be used as light source and come for the back light unit of LCD or as the light illuminating unit in illuminated field back light unit.In general, there are side entrance back unit and direct-type backlight unit in the position of root Ju light source.Due to the mechanical property of their excellences, the resin combination of thermoplastic polymer is used to the goods manufacturing various size and shape, includes but not limited to base member and shell.In many cases, due to snappiness and their low cost of design, polymer resin composition is alternative metals in such applications.But these application many need parts near thermal source such as electric light source or contact with it.Therefore, expect to form these parts by abundant heat conduction with the material distributed by the heat of generation.Need and there is the thermally conductive material of light reflectivity to control the directional characteristic of light in backlight framework or LCD base (being in particular 3D LCD).Therefore, the heat-conductive resin composition with light reflectivity can ideally in the base of backlight framework or that LCD.Attempting to improve in thermal conduction characteristic, conventional practice is add thermally conductive material in thermoplastic compounds always.United States Patent (USP) 6487073 describes the case of distribute heat from electronic installation, described electronic installation comprises the shell of the mouldable heat-conductive composite material of net type of the polymer base material matrix with heat conductive filler, and with the intercommunication of electronic component heat, wherein heat is from also distributing through the electronic component producing heat.Openly not there is the example of the resin combination of light reflectivity.
Other performance expected for LCD structure parts comprises light reflectivity.Such as, United States Patent (USP) 7235918 describes the molding reverberator goods being coated with luminous reflectance metal and the resin combination for described goods, and described resin combination comprises matrix polymer matrix and heat conduction carbon material.But, openly not there is the example of high heat conductance and low reflection.
As mentioned above, although some conventional material comprising the structure of some goods has proved to be applicable to LCD structure parts, researching and developing the material having a combination of high heat conductance and light reflectivity than conventional material will be useful.For LCD structure parts and other application, this type of material is by the light reflectivity of the thermal conductivity and expectation that provide improvement.
Summary of the invention
Disclosed herein is and claimed molded thermoplastic product, described goods comprise one or more thermoplastic polymers of (a) about 19.5 to about 79.5 % by weight; The filler of (b) about 20 to about 80 % by weight, the thermal conductivity of described filler is at least 5W/mK; The carbon black powder of (c) about 0.5 to 10 % by weight; (d) at least one fibrous packing of 0 to about 30 % by weight, described fibrous packing has the thermal conductivity being no more than 5W/mK; The moulded parts wherein prepared by described thermoplastic compounds have 400nm and 700nm wavelength use Spectrophotometric be no more than 10% luminous reflectance factor, and there is the thermal conductivity of at least 1W/mK using laser pulse method to measure according to ASTM E1462.
Moulded parts of the present invention especially can be used for electronics and electrical equipment, comprise in the application of the understructure of Electrical and Electronic device, wherein light source is in internal build, and wherein heat produces to distribute heat in ambient air in light source, and have the thermal conductivity performance of improvement, it is made up of heat conduction thermoplastic resin composition.Preferred application relates to the light source being used as LCD back light unit or the luminous package being used as the light illuminating unit in illuminated field back light unit.Other side of the present invention and embodiment will better be understood according to the embodiment of following preferred embodiment.
Embodiment
thermoplastic polymer (a)
Thermoplastic polymer is the polymeric matrix of composition, and wherein one or more polymkeric substance are used in external phase.Available thermoplastic polymer comprises thermoplastic polyester, polymeric amide, polycarbonate, polyphenylene oxide, poly arylidene thio-ester, liquid crystalline polymers and syndiotactic polystyrene and their blend.Preferred thermoplastic polymer is polyester, polymeric amide, liquid crystalline polymers and poly arylidene thio-ester, because their higher rigidity, better mouldability and flame retardant resistance are the important requirement of frame material in the present patent application.
The preferred thermoplastic polyester of the present invention comprises the polyester with 0.3 or larger limiting viscosity, and is glycol and di-carboxylic acid in general, or the saturated condensation product of the straight chain of its reactive derivatives.They preferably comprise the condensation product of aromatic dicarboxylate and at least one glycol with 8 to 14 carbon atoms, and described glycol is selected from neopentyl glycol, cyclohexanedimethanol, 2，2-dimethyl-1，3-propanediol and has formula HO (CH
2)
nthe aliphatic diol of OH structure, wherein n is the integer of 2 to 10.The glycol of maximum 20 % by mole can be aromatic diol, as with trade(brand)name
the 220 Ethoxylated bisphenol A sold by Akzo Nobel Chemicals, Inc.; Resorcinol; '-biphenyl diphenol; Or dihydroxyphenyl propane.The aromatic dicarboxylate of maximum 50 % by mole can be substituted by the different aromatic dicarboxylates that at least one has 8 to 14 carbon atoms, and/or the aromatic dicarboxylate of maximum 20 % by mole can be substituted by the aliphatic dicarboxylic acid with 2 to 12 carbon atoms.Multipolymer can react equivalent by two or more glycol or its reaction equivalent and at least one di-carboxylic acid or its to be prepared, or reacts equivalent and at least one glycol or its by two or more di-carboxylic acid or its and react equivalent and prepare.Bifunctional hydroxy's acid mono such as hydroxy-benzoic acid or hydroxynaphthoic acid or their reaction equivalent also can be used as comonomer.
Preferred polyester comprises poly-(ethylene glycol terephthalate) (PET), poly-(terephthalic acid 1,4-butanediol ester) (PBT), poly-(terephthalic acid 1, ammediol ester) (PPT), poly-(2,6-naphthalene diacid 1,4-butanediol ester) (PBN), poly-(2,6-naphthalene diacid glycol ester) (PEN), poly-(terephthalic acid 1,4 cyclohexane dimethanol ester) (PCT) and above-mentioned multipolymer and mixture.The multipolymer of further preferably terephthalic acid 1,4 cyclohexane dimethanol ester/m-phthalic acid 1,4 cyclohexane dimethanol ester and other straight chain homopolymer ester derived from aromatic dicarboxylate and glycol, described aromatic dicarboxylate comprises m-phthalic acid; Diphenic acid; Comprise 1,5-; 2,6-; With the naphthalic acid of 2,7-naphthalic acid; 4,4 '-biphenyl dicarboxylic acid; Two (to carboxyl phenyl) methane; Ethylenebis (to carboxyl benzene); Two (to carboxyl phenyl) BDO ether; Two (to carboxyl phenyl) glycol ether; Two (to carboxyl phenyl) 1,3-PD ether; With two (to carboxyl phenyl) BDO ether, described glycol is selected from 2，2-dimethyl-1，3-propanediol; Neopentyl glycol; Cyclohexanedimethanol; And there is general formula HO (CH
2)
nthe aliphatic diol of OH structure, wherein n is the integer of 2 to 10, such as ethylene glycol; 1,3-PD; BDO; 1,6-hexylene glycol; 1,8-ethohexadiol; Decamethylene-glycol; 1,3-PD; And BDO.As described above, one or more aliphatic acids of maximum 20 % by mole can be there are, comprise hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid or 1,4 cyclohexanedicarboxylic acid.The multipolymer of equivalent is further preferably reacted derived from BDO, Ethoxylated bisphenol A and terephthalic acid or its.The further preferably random copolymers of at least two kinds in PET, PBT and PPT, and the mixture of at least two kinds and the mixture of any above-mentioned substance in PET, PBT and PPT.
Thermoplastic polyester also can be the multipolymer form comprising poly-(alkylene oxide) soft chain segment (block).The sulfur-bearing of poly-(alkylene oxide) segment is the every 100 parts per weight of thermoplastic's polyester of about 1 to about 15 weight part.Poly-(alkylene oxide) segment has the number-average molecular weight in about 200 to about 3,250 scopes, or preferably has the number-average molecular weight in about 600 to about 1,500 scopes.Preferred multipolymer comprises poly-(oxyethane) and/or poly-(butyleneglycol) that is mixed in PET or PBT chain.Embedding grammar is well known by persons skilled in the art, and uses poly-(alkylene oxide) soft chain segment during can being included in polyreaction as comonomer to form polyester.PET can gather the copolymer blended of (alkylene oxide) with PBT and at least one.Poly-(oxirane) also can be copolymer blended with PET/PBT.The crystallization rate can accelerating described polyester in the polyester portion of described composition is incorporated into by gathering (alkylene oxide) soft chain segment.
Preferred polymeric amide comprises semicrystalline polyamides and amorphous polymeric amide.
Described semicrystalline polyamides comprises aliphatic series or half aromatics semicrystalline polyamides.
Described semi-crystalline aliphatic polyamide can derived from aliphatic series and/or alicyclic monomer, such as one or more hexanodioic acids, sebacic acid, nonane diacid, dodecanedioic acid or their derivative etc., aliphatic C
6-C
20alkylenediamine, alicyclic diamine, lactan and amino acid.Preferred diamines comprises bis(p-aminocyclohexyl) methane; Hexamethylene-diamine; 2 methyl pentamethylenediamine; 2-methyl octamethylenediamine; Trimethylhexamethylenediamine; 1,8-octamethylenediamine; 1,9-nonamethylene diamine; 1，10-diaminodecane; 1,12-diamino dodecane; With m-xylene base diamines.Preferred lactan or amino acid comprise 11-aminododecanoic acid, hexanolactam and laurolactam.
Preferred aliphatic polyamide comprises polyamide 6; Polyamide 6,6; Polymeric amide 4,6; Polyamide 6,10; Polyamide 6,12; Polymeric amide 11; Polymeric amide 12; Polymeric amide 9,10; Polymeric amide 9,12; Polymeric amide 9,13; Polymeric amide 9,14; Polymeric amide 9,15; Polyamide 6,16; Polymeric amide 9,36; Polymeric amide 10,10; Polymeric amide 10,12; Polymeric amide 10,13; Polymeric amide 10,14; Polymeric amide 12,10; Polymeric amide 12,12; Polymeric amide 12,13; Polymeric amide 12,14; Polyamide 6,14; Polyamide 6,13; Polyamide 6,15; Polyamide 6,16; And polyamide 6,13.
Described half aromatics semicrystalline polyamides is derived from one or more homopolymer containing aryl monomer, multipolymer, terpolymer or high polymer.The example comprising aryl monomer is terephthalic acid and derivative thereof.Preferably the monomer for the preparation of the present invention's aromatic polyamide used of about 5 % by mole to about 75 % by mole comprises aryl, and more preferably from about the described monomer of 10 % by mole to about 55 % by mole comprises aryl.
The example of preferred semi-crystalline semi-aromatic polyamide comprises poly-(m xylylene adipamide) (polymeric amide MXD, 6), poly-(paraphenylene terephthalamide 12 carbon diamines) (polymeric amide 12, T), poly-(paraphenylene terephthalamide's decamethylene diamine) (polymeric amide 10, T), poly-(paraphenylene terephthalamide's nonamethylene diamine) (polymeric amide 9, T), hexamethylene adipamide/hexamethylene terephthalamide copolyamide (polyamide 6, T/6,6), hexamethylene terephthalamide/paraphenylene terephthalamide-2 methyl pentamethylenediamine copolyamide (polyamide 6, T/D, T); Hexamethylene adipamide/hexamethylene terephthalamide/6I hexamethylene isoterephalamide copolyamide (polyamide 6,6/6, T/6, I); Poly-(hexanolactam-hexamethylene terephthalamide) (polyamide 6/6, T) etc.
Preferred semi-crystalline semi-aromatic polyamide is selected from and comprises hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine copolyamide (polyamide 6, T/D, T), and preferably there is 45-55 % by mole of repeating unit 6, T and 55-45 % by mole of repeating unit D, T.
In the present invention, according to thermotolerance at high temperature, dimensional stability and moistureproofness, semi-crystalline semi-aromatic polyamide is preferred.
Semi-crystalline semi-aromatic polyamide derived from the monomer comprising aryl is particularly advantageous in the application for needing polyamide compositions physical performance (as mechanical property, moistureproofness, thermotolerance etc.) balance and higher heat-conductivity.
In the present invention, amorphous polymeric amide can be used to can not bring significant negative impact to performance in polymer composition.They are derived from one or more homopolymer comprising m-phthalic acid and/or dimethyl diamino-dicyclohexyl methane group, multipolymer, terpolymer or high polymer.
In described preferred amorphous polyamide, described polymeric amide is made up of the polymkeric substance of repeating unit or multipolymer with derived from carboxylic acid component and aliphatic diamine component.Described carboxyl acid component is the mixture of m-phthalic acid or m-phthalic acid and one or more other carboxylic acids, and wherein based on described carboxyl acid component, described carboxyl acid component comprises the m-phthalic acid of at least 55 % by mole.Terephthalic acid and hexanodioic acid can be comprised by other carboxylic acid used in described carboxyl acid component.Described aliphatic diamine component is the mixture of hexanediamine or hexanediamine and 2 methyl pentamethylenediamine and/or 2-ethyl butanediamine, and wherein based on described aliphatic diamine component, described aliphatic diamine component comprises the hexanediamine of at least 40 % by mole.
The example of preferred amorphous polyamide comprises: poly-(hexamethylene terephthalamide/6I hexamethylene isoterephalamide) (polyamide 6, T/6, I), poly-(6I hexamethylene isoterephalamide) (polyamide 6, I), poly-(mpd-i/6I hexamethylene isoterephalamide) (polymeric amide MXD, I/6, I), poly-(mpd-i/paraphenylene terephthalamide's mphenylenediamine/6I hexamethylene isoterephalamide) (polymeric amide MXD, I/MXD, T/6, I/6, T), poly-(mpd-i/isophthaloyl dodecamethylene diamine) (polymeric amide MXD, I/12, I), poly-(mpd-i) (polymeric amide MXD, I), poly-(isophthaloyl dimethyl diamino-dicyclohexyl methane/lauramide) (polymeric amide MACM, I/12), poly-(isophthaloyl dimethyl diamino-dicyclohexyl methane/paraphenylene terephthalamide's dimethyl diamino-dicyclohexyl methane/lauramide) (polymeric amide MACM, I/MACM, T/12), poly-(6I hexamethylene isoterephalamide/isophthaloyl dimethyl diamino-dicyclohexyl methane/lauramide) (polyamide 6, I/MACM, I/12), poly-(6I hexamethylene isoterephalamide/hexamethylene terephthalamide/isophthaloyl dimethyl diamino-dicyclohexyl methane/paraphenylene terephthalamide's dimethyl diamino-dicyclohexyl methane) (polyamide 6, I/6, T/MACM, I/MACM, T), poly-(6I hexamethylene isoterephalamide/hexamethylene terephthalamide/isophthaloyl dimethyl diamino-dicyclohexyl methane/paraphenylene terephthalamide's dimethyl diamino-dicyclohexyl methane/lauramide) (polyamide 6, I/6, T/MACM, I/MACM, T/12), poly-(isophthaloyl dimethyl diamino-dicyclohexyl methane/dodecane two acyl dimethyl diamino-dicyclohexyl methane) (polymeric amide MACM, I/MACM, 12), and their mixture.
When using amorphous polymeric amide, based on the hypocrystalline of existence and the total amount of amorphous polyamide, semicrystalline polyamides exists with about 40 to about 100 (and preferred about 70 to about 100) % by weight.
Poly arylidene thio-ester can be the compound of straight chain, a kind of under high temperature and oxygen exist through being subject to processing the compound carrying out being cross-linked, a kind of multi-halogenated compounds by adding three a small amount of halos or more is introduced in wherein and has the compound of the crosslinked of a tittle or branched structure, one stands heat treated compound in non-oxidizing inert gas such as nitrogen, or the mixture of these structures.
LCP is anisotropic polymkeric substance when referring to and use TOT test or its any reasonable variation to test, as United States Patent (USP) 4, and 118, described in 372, described document is incorporated to herein by reference.Available LCP comprises polyester, poly-(ester-acid amide) and poly-(ester-imide).A kind of preferred form of LCP is " full aromatics " form, and all groups namely in main polymer chain are aryl (connecting except base, such as ester group), but can there is non-aromatic side base.
In a preferred embodiment, based on the total weight of described composition, thermoplastic polymer is included with the amount of about 19.7 to about 79.7 % by weight.Preferably, thermoplastic polymer with about 35 % by weight to about 65 % by weight amount be included.
heat conductive filler (b)
Heat conductive filler used in the present invention is not particularly limited, as long as the thermal conductivity of filler is at least 5W/mK, and preferably at least 10W/mK, and also more preferably 100W/mK.Available heat conductive filler is selected from the oxide powder, thin slice and the fiber that are made up of aluminum oxide (alumina), zinc oxide, magnesium oxide and silicon-dioxide; The nitride powder be made up of boron nitride, aluminium nitride and silicon nitride, thin slice and fiber; By gold and silver, aluminium, iron, copper, tin, the metal formed as the tin-based alloy of lead-free solder and metal alloy powders, thin slice and fiber; Carbon fiber, graphite; Silicon carbide powder; Zinc sulphide, magnesiumcarbonate and Calcium Fluoride (Fluorspan) powder etc.Should describe " by ... composition ", in general, with " comprising ", there is identical implication.These fillers can be used independently, and maybe can use the combination of they two or more.Preferred heat conductive filler is selected from magnesium oxide, graphite, carbon fiber, Calcium Fluoride (Fluorspan) powder, magnesiumcarbonate, boehmite; And especially preferred heat conductive filler is graphite.
When graphite is used as component (b), graphite can be artificial or natural formation, as long as it has lamella shape.
The graphite of the natural formation of commercially available acquisition has three types.They are that flake graphite, amorphous graphite and crystal mineral ore graphite are using the graphite as natural formation.
Just as the name indicates, flake graphite has lamellar form.Amorphous graphite is not really unbodied as its name implies, but in fact crystallization.Crystal mineral ore graphite has vein sample outward appearance in general on its outer surface, derives its title thus.
Synthetic graphite can produce by coke and/or derived from the pitch of oil or coal.Synthetic graphite is purer than natural graphite, but for crystallization.
Flake graphite and the crystal mineral ore graphite of natural formation are preferred according to thermal conductivity and dimensional stability, and flake graphite is preferred.
Heat conductive filler (b) can have size-grade distribution widely.If packing material size is too small, then the viscosity of resin can be increased to a certain degree in blended period, so that cannot realize the dispersion completely of filler.Therefore, the resin with high heat conductance can not be obtained.If the particle diameter of filler is excessive, then during the thin narrow portion that heat-conducting resin can not be injected into resin injection chamber is divided, be especially associated with thermal transpiration component those.Preferably, maximum mean size is less than 300 microns, is also more preferably less than 200 microns.As used AccuSizer Model780A (particle instrument, Santa Barbara, CA), have such as by using, Selas Granulometer " 920 type " or the laser diffraction type size distribution of laser diffraction and scattering method size distribution measuring apparatus " LS-230 " of being produced by Coulter K.K. are measured.Preferably, mean particle size between 1 micron to 100 microns, more preferably between 5 microns to 80 microns.Its granularity also can be used to have particulate or the particle of multiple grain size distribution pattern.Especially preferred heat conductive filler is for having about 5 to about 100 microns, and the graphite flake of preferred about 20 to about 80 micron granularities.
Heat conductive filler or thermal conductivity are less than the available coupling agent treatment in surface of the fibrous packing of 5W/mK (as hereafter disclosed), to reach the object improving interfacial adhesion between filling surface and matrix resin.The example of coupling agent comprises silane series, titanate series, zirconate series, aluminate serial and aluminium zirconate series coupling agent.
Available coupling agent comprises metal hydroxides and alkoxide, comprises those and lanthanon of periodic table of elements IIIa race to VIIIa race, Ib race, IIb race, IIIb race and IVb race.Concrete coupling agent is the alkoxide of metal hydroxides and metal, and described metal is selected from Ti, Zr, Mn, Fe, Co, Ni, Cu, Zn, Al and B.Preferred metal hydroxides and alkoxide are those of Ti and Zr.Concrete metal alkoxide coupling agent is ortho ester and the inner complex of titanate and zirconate, comprises the compound of formula (I), (II) and (III):
Wherein
M is titanium or zirconium;
R is monovalence C
1-C
8straight chain or branched-alkyl;
Y is divalent group, is selected from-CH (CH
3)-,-C (CH
3)=CH
2-or-CH
2cH
2-;
X is selected from OH ,-N (R
1)
2,-C (O) OR
3,-C (O) R
3,-CO
2 -a
+; Wherein
R
1for-the CH be optionally optionally substituted by a hydroxyl group or interleave by ether oxygen
3or C
2-C
4straight chain or branched-alkyl; Precondition is no more than a heteroatoms and is bonded on any one carbon atom;
R
3for C
1-C
4straight chain or branched-alkyl;
A
+be selected from NH
4 +, Li
+, Na
+, or K
+.
Coupling agent can join in described filler before filler and mixed with resin, or can add while filler and resin alloy.The add-on of coupling agent is preferably 0.1 to 5 % by weight relative to the weight of filler, or preferably 0.5 to 2 % by weight.During filler and resin alloy, add coupling agent have and to improve in connecting surface fusible additional advantage between metal used, described connecting surface is between heat transfer unit or between thermal transpiration unit and heat-conducting resin.
In thermoplastic compounds, the content of heat conductive filler 20 to 80 % by weight, and preferably 30 to 70 % by weight, also more preferably in 40 to 60 % by weight scopes, wherein weight percent is the gross weight based on the described thermoplastic compounds of heat.
carbon black powder (c)
In the present invention, such as, carbon black powder (c) is furnace treated black, thermally oxidized black or acetylene black, preferably has and is less than that of 100nm mean particle size, also more preferably have and be less than that of 20nm mean particle size.
In the present invention, can use is not the blackish pigment of carbon black, such as black chromium sesquioxide, titanium are black, black iron oxide, black pigment dyestuff, such as nigrosine and the mixing pigment dyestuff that obtained by the pigment dyestuffs that mixing at least two kinds is selected from redness, blueness, green, violet, yellow, cyan and magenta pigment, to show artificial black.
In thermoplastic compounds, the content of carbon black powder (c) is in 0.5 to 10 % by weight scope, and preferably 0.6 to 3 % by weight, and also more preferably 0.8 to 2 % by weight, wherein weight percent is the gross weight based on the described thermoplastic compounds of heat.
fibrous packing (d)
The fibrous packing being no more than 5W/mK thermal conductivity that has being used as component (d) is in the present invention pin sample filamentary material.The example of preferred fibrous packing comprises wollastonite (calcium silicate whisker), glass fibre, aluminum borate fiber, calcium carbonate fiber and potassium titanate fiber.Preferred fibrous packing is glass fibre.
Fibrous packing preferably will have at least 5, or more preferably at least 10 weighted mean long-width ratio.When deployed, based on the total weight of described composition, optional fibrous packing preferably with about 5 to about 30 % by weight, or more preferably will exist with about 10 to about 20 % by weight.Fibrous packing can improve physical strength in mold component face and thermal conductivity, its key property needed for frame material.
The polymer toughening agent being optionally used as component (e) is in the present invention to the effective any toughner of thermoplastic polymer used.
When described thermoplastic polymer is polyester, described toughner is generally elastomerics or has lower fusing point, general < 200 DEG C, preferably 150 DEG C, and it is connected with the functional group can reacted with described thermoplastic polyester (and other polymkeric substance optionally existed).Because thermoplastic polyester has carboxyl and hydroxyl usually, therefore these functional groups generally can with carboxyl and/or hydroxyl reaction.The example of this type of functional group comprises epoxy group(ing), carboxylic acid anhydride, hydroxyl (alcohol), carboxyl and isocyanate group.Preferred functional group is epoxy group(ing) and carboxylic acid anhydride, and especially preferred epoxy group(ing).General by small molecules is grafted on already present polymkeric substance, or when polymer toughening agent molecule is prepared by copolyreaction, comprised the monomer of required functional group by copolymerization, this type of functional group can be made " to be connected to " in polymer toughening agent.As an example of grafting, free radical grafting technology can be adopted by maleic anhydride graft on hydrocarbon rubbers.The graftomer of gained has connected carboxylic acid anhydride and/or carboxylic group.For functional group's copolymerization polymer toughening agent in the polymer, its example is ethene and the multipolymer of (methyl) acrylate monomer comprising suitable functional group.It can be the compound of acrylate, methacrylic ester or the two mixture that so-called (methyl) acrylate in this article refers to.Available (methyl) acrylate functional compound comprises (methyl) vinylformic acid, (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) glycidyl acrylate and (methyl) vinylformic acid-2-isocyanato ethyl.Except ethene and functionalized (methyl) acrylate monomer, also can by other monomer copolymerization in this polymkeric substance, if vinyl-acetic ester, unfunctionalized (methyl) acrylate are as (methyl) ethyl propenoate, (methyl) n-butyl acrylate and (methyl) cyclohexyl acrylate.Preferred toughner comprises lists in United States Patent (USP) 4,753, those in 980.Especially preferred toughner is the multipolymer of ethene, ethyl propenoate or n-butyl acrylate and glycidyl methacrylate.
The polymer toughening agent used together with thermoplastic polyester preferably comprises about 0.5 % by weight to about 20 % by weight, preferably about 1.0 % by weight to about 15 % by weight, more preferably from about 7 % by weight to about 13 % by weight containing monomer.In polymer toughening agent, the functionalized monomer of a more than class can be there is.Find, the toughness of described composition can be increased by the amount of the amount and/or functional group that increase polymer toughening agent.But this tittle preferably should can not increase to the crosslinkable degree of described composition, especially before the final component shape of acquisition.
The polymer toughening agent used together with thermoplastic polyester can also be not the thermoplastic acrylic polymer of ethylene copolymer.Described thermoplastic acrylic copolymer obtains by being polymerized following material: vinylformic acid, acrylate is (as methyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, the just own ester of vinylformic acid, and n-octyl), methacrylic acid and methacrylic ester are (as methyl methacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA (BA), Propenoic acid, 2-methyl, isobutyl ester, n-amylmethacrylate, n octyl methacrylate, glycidyl methacrylate (GMA) etc.).Also can use the multipolymer derived from two or more the above-mentioned type monomers, and by multipolymer prepared by the polyreaction of one or more the above-mentioned type monomer and vinylbenzene, vinyl cyanide, divinyl, isoprene etc.In these multipolymers, part or all components should preferably have not higher than the second-order transition temperature of 0 DEG C.For preparation thermoplastic acrylic polymer toughner, preferred monomer is the just own ester of methyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, vinylformic acid and n-octyl.
Thermoplastic acrylic polymer toughner preferably has core-shell structure.Described core-shell structure is that wherein core segment preferably has 0 DEG C or lower second-order transition temperature, and shell part preferably has the structure of the second-order transition temperature higher than the second-order transition temperature of described core segment.
Available polysiloxane grafted described core segment.Available low surface energy substrates is shell part as described in the grafting such as siloxanes, fluorine.The acrylic polymers with core-shell structure by the thermoplastic polyester in the present composition and between other component mixing period or afterwards with himself agglomeration, and be easy in the composition dispersed, described core-shell structure has grafting low surface energy substrates on said surface.
The toughner being applicable to polymeric amide is described in United States Patent (USP) 4,174, in 358.Preferred toughner comprises the polyolefine with compatibilizing agent modification, and described compatibilizing agent is as acid anhydrides, di-carboxylic acid or derivatives thereof, carboxylic acid or derivatives thereof and/or epoxide group.Compatibilizing agent is introduced by unsaturated acid anhydride, di-carboxylic acid or derivatives thereof, carboxylic acid or derivatives thereof and/or epoxide group being grafted on polyolefine.Also can be introduced by described compatibilizing agent when described polyolefine is prepared by monomer copolymerization, described monomer comprises undersaturated acid anhydrides, di-carboxylic acid or derivatives thereof, carboxylic acid or derivatives thereof and/or epoxide group.Described compatibilizing agent preferably comprises 3 to 20 carbon atoms.Can the example of grafting (or can be used as comonomer with preparation) polyolefinic typical compound be vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride and citraconic anhydride.
When deployed, based on the total weight of described composition, optional polymer toughening agent preferably with about 2 to about 15 % by weight, or more preferably will exist with about 5 to about 15 % by weight.
Composition as herein described optionally comprises one or more toughner suitable to thermoplastic polymer used.Two (2 ethyl hexanoic acid) PEG 400 ester, (2 ethyl hexanoic acid) methoxyl group PEG 550 ester and two (2 ethyl hexanoic acid) four (ethylene glycol) etc. are comprised for the softening agent that thermoplastic polyester is suitable.When deployed, based on the total weight of described composition, softening agent will preferably exist with about 0.5 to about 5 % by weight.
When the thermoplastic polymer for composition as herein described is polyester, composition also optionally comprises one or more nucleators, the sodium salt, Sodium Benzoate etc. of the sodium salt of the organic polymer of such as carboxylation or sylvite, longer chain fatty acid.Polyester partly or entirely can be replaced the polyester with end group, one of them is neutralized by sodium or potassium a bit.When deployed, based on the total weight of described composition, softening agent will preferably exist with about 0.1 to about 4 % by weight.
In electrical equipment and electron device, flame retardant resistance is the important requirement of frame material.Therefore, composition as herein described also optionally comprises one or more fire retardants.Suitable fire retardant includes but not limited to the epoxide of the cinnamic polymkeric substance of the polystyrene of bromination, bromination, bromination, the polycarbonate of bromination, poly-(pentabromobenzyl acrylate) and metal phosphinate salt.When deployed, based on the total weight of described composition, fire retardant will preferably exist with about 3 to about 20 % by weight.The composition comprising fire retardant also can comprise one or more flame retardant synergist, such as, but not limited to sodium antimonate and weisspiessglanz.
Thermoplastic resin composition as herein described in addition to the foregoing, also optionally comprises additive, such as thermo-stabilizer, antioxidant, dyestuff, mould stripper, lubricant, ultra-violet stabilizer, (paint) adhesionpromoter etc.When deployed, based on the total weight of described composition, aforementioned additive will preferably in combination exist with about 0.1 to about 5 % by weight.
Composition as herein described is the blend of melting mixing, and wherein all polymeric constituents are dispersed in each other, and all non-polymeric constituents are dispersed and be wrapped in polymeric matrix, makes described blend form homogeneous entirety.The each constituent materials of any melting mixing Combination of Methods can be adopted to obtain blend.Melting mixing machine can be used as singe screw or twin screw extruder, blender, kneader, Banbury mixer etc., these constituent materialss are mixed, to obtain resin combination.Portion of material can be mixed in melting mixing machine, then add surplus material, and further melting mixing is until evenly.As skilled in the art will appreciate, in the preparation of thermal conductive polymer resin combination of the present invention, the order of mixing can be: each component of melting once, or by filler and/or the charger charging from the side of other component etc.
Composition as herein described can use method known to those skilled in the art, such as such as injection moulding, blowing or extrude formation goods.This based article can comprise for those of the lampshade of motor case, lampshade, automobile and other vehicle and Electrical and Electronic device outer case.Automobile is headlight and taillight with the example of the lampshade in other carrier, comprises head lamp, taillight and brake lamp, especially uses photodiode (LED) bulb those.In numerous applications, described goods can be used as by the surrogate of the goods of aluminium or other preparation of metals.
example
Chemical combination and molding methods: prepare the polymer composition be shown in Table 1 by compounding in 32mm Werner and Pfleiderer twin screw extruder.All compositions are blended into together and add the rear portion of forcing machine to, unlike graphite by side-fed to the downstream of screw rod cylinder.Barrel temperature is set at about 315 DEG C, causes the melt temperature of 330 DEG C.
Described composite mold is moulded ISO test sample book, molding on injection molding machine, to measure mechanical property.In order to measurement of reflectivity and thermal conductivity, they are molded as the plate of the sheet with 1mm × 60mm × 60mm size.Melt temperature is about 320 DEG C, and die temperature is 150 DEG C.
Use ISO527-1/2 standard method test tensile strength and elongation.ISO178-1/2 standard method is used to measure flexural strength and modulus.ISO179/1eA standard method is used to measure Notched Charpy impact intensity.Above-mentioned test is implemented at 23 DEG C.Result is shown in Table 1.
Thermal conductivity uses as the laser pulse method described in ASTM E1461 is measured at in-plane.Result is shown in Table 1.
The spectrophotometer Datacolor of reflectivity by being manufactured by Datacolor
measure.Instrument is that PC drives, and the explanation being programmed to follow manufacturers is driven, with measurement of reflectivity information.Result is shown in Table 1.
Following term is used in table 1:
hTN:
hTN501, copolyamide 6, T/D, T, by E.I.du Pont de Nemoursand Co., Wilmington, DE produce.
graphiterefer to graphite flake CB-150, there is the mean particle size of 40 μm, supplied by NipponGraphite Industries, Ltd..
cBrefer to carbon black powder, BLACK
900, there is the mean particle size of 15nm, supplied by Cabot Corporation.
talcum powderrefer to talcum powder LMS-200, there is the mean particle size of 5 μm, supplied by Fuji TalcIndustrial Co.Ltd..
2,6-NDA: NDA, supplied by BP Amoco Chemical Company.
hSrefer to the thermo-stabilizer comprising copper halide (I) and potassium halide.
lubricantrefer to Licowax OP, supplied by Clariant Japan.K.K.
table 1
Claims (9)
1. the thermoplastic article of molding, comprises:
One or more thermoplastic polymers of (a) 19.5 to 79.5 % by weight;
The filler of (b) 20 to 80 % by weight, the thermal conductivity of described filler is at least 5W/mK;
The carbon black powder of (c) 0.5 to 10 % by weight, it has the mean particle size being less than 100nm; With
The fibrous packing of (d) 0 to 30 % by weight, described fibrous packing has the thermal conductivity being no more than 5W/mK;
The moulded parts wherein prepared by described thermoplastic compounds have 400nm and 700nm wavelength use Spectrophotometric be no more than 10% luminous reflectance factor, and there is the thermal conductivity of at least 1W/mK using laser pulse method to measure according to ASTM E1461.
2. molded thermoplastic product according to claim 1, one or more heat conductive fillers (b) wherein said are independently selected from Calcium Fluoride (Fluorspan), magnesium oxide, magnesiumcarbonate, boehmite, graphite flake and carbon fiber.
3. molded thermoplastic product according to claim 2, the graphite flake of mean particle size of wherein said heat conductive filler (b) for having 5 to 100 μm.
4. molded thermoplastic product according to claim 1, wherein said fibrous packing (d) is glass fibre.
5. molded thermoplastic product according to claim 1, one or more thermoplastic polymers (a) wherein said are independently selected from thermoplastic polyester, polymeric amide, polycarbonate, polyphenylene oxide, poly arylidene thio-ester, liquid crystalline polymers and syndiotactic polystyrene.
6. molded thermoplastic product according to claim 5, one or more thermoplastic polymers (a) wherein said comprise semi-crystalline semi-aromatic polyamide, described semi-crystalline semi-aromatic polyamide is selected from hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine copolyamide (polyamide 6, T/D, T).
7. molded thermoplastic product according to claim 1, the thermal conductivity of wherein said polymer composition is higher than 3W/mK.
8. molded thermoplastic product according to claim 1, also comprises the polymer toughening agent of (e) 2 to 15 % by weight.
9. molded thermoplastic product according to claim 1, comprises framework or the base of the LED-backlit framework of LCD.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201061424796P | 2010-12-20 | 2010-12-20 | |
| US61/424796 | 2010-12-20 | ||
| US61/424,796 | 2010-12-20 | ||
| PCT/US2011/066333 WO2012088207A2 (en) | 2010-12-20 | 2011-12-20 | Molded thermoplastic articles comprising thermally conductive polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103270099A CN103270099A (en) | 2013-08-28 |
| CN103270099B true CN103270099B (en) | 2015-03-11 |
Family
ID=45464925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180061463.3A Expired - Fee Related CN103270099B (en) | 2010-12-20 | 2011-12-20 | Molded thermoplastic articles comprising thermally conductive polymers |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20120157600A1 (en) |
| JP (1) | JP2014503658A (en) |
| CN (1) | CN103270099B (en) |
| WO (1) | WO2012088207A2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150232664A1 (en) * | 2012-09-07 | 2015-08-20 | Sabic Innovative Plastics Ip B.V. | Thermally conductive blended polymer compositions with improved flame retardancy |
| US9434870B2 (en) | 2012-09-19 | 2016-09-06 | Momentive Performance Materials Inc. | Thermally conductive plastic compositions, extrusion apparatus and methods for making thermally conductive plastics |
| US20140080951A1 (en) * | 2012-09-19 | 2014-03-20 | Chandrashekar Raman | Thermally conductive plastic compositions, extrusion apparatus and methods for making thermally conductive plastics |
| JP6316556B2 (en) * | 2013-08-29 | 2018-04-25 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Electrically insulating and thermally conductive polymer composition |
| FR3012571B1 (en) * | 2013-10-29 | 2016-02-05 | Astrium Sas | MATERIAL AND DEVICE FOR CONTAINING CRYOGENIC LIQUIDS |
| CN104497538B (en) * | 2014-12-31 | 2016-10-05 | 东莞市松燊塑料科技有限公司 | A kind of antistatic PC is material modified and preparation method thereof |
| CN107924908B (en) | 2015-07-13 | 2020-10-23 | 莱尔德电子材料(深圳)有限公司 | Thermal management and/or EMI mitigation materials with custom colored exterior surfaces |
| US10717911B2 (en) | 2015-10-09 | 2020-07-21 | Ineos Styrolution Group Gmbh | Electrically conducting thermally conductive polymer resin composition based on styrenics with balanced properties |
| WO2017060344A1 (en) | 2015-10-09 | 2017-04-13 | Ineos Styrolution Group Gmbh | Thermally conductive polymer resin composition based on styrenics with low density |
| WO2017060347A1 (en) | 2015-10-09 | 2017-04-13 | Ineos Styrolution Group Gmbh | Electrically insulating thermally conductive polymer resin composition based on styrenics with balanced properties |
| WO2017136196A1 (en) | 2016-02-01 | 2017-08-10 | Cabot Corporation | Thermally conductive polymer compositions containing carbon black |
| PL3523371T3 (en) * | 2016-10-06 | 2021-06-14 | Struers ApS | A thermoplastic mounting medium and a method of its manufacture |
| CN108164970A (en) * | 2016-12-07 | 2018-06-15 | 上海杰事杰新材料(集团)股份有限公司 | Low dielectric polyphenylene oxide composite material of a kind of high heat conduction and preparation method thereof |
| CN108164953A (en) * | 2016-12-07 | 2018-06-15 | 上海杰事杰新材料(集团)股份有限公司 | Low dielectric polycarbonate composite material of a kind of high heat conduction and preparation method thereof |
| EP3527615A1 (en) | 2018-02-16 | 2019-08-21 | Venator Germany GmbH | Thermoconductive filler particles and polymer compositions containing them |
| WO2023190965A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社Ｎｂｃメッシュテック | Antibacterial/antiviral resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040251804A1 (en) * | 2003-06-11 | 2004-12-16 | Cool Options, Inc. | Thermally-conductive plastic articles having light reflecting surfaces |
| CN101861353A (en) * | 2007-11-16 | 2010-10-13 | 纳幕尔杜邦公司 | Thermally conductive resin compositions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753A (en) | 1846-09-10 | Improvement in artificial millstones | ||
| US980A (en) | 1838-10-13 | Improvement in the mode of hardening or chilling the hubs of car and other wheels | ||
| PH15509A (en) | 1974-05-10 | 1983-02-03 | Du Pont | Improvements in an relating to synthetic polyesters |
| US4174358A (en) | 1975-05-23 | 1979-11-13 | E. I. Du Pont De Nemours And Company | Tough thermoplastic nylon compositions |
| US4248763A (en) * | 1978-07-22 | 1981-02-03 | Daikin Kogyo Co., Ltd. | Fluorine-containing resin composition having improved thermal stability |
| US6487073B2 (en) | 1999-12-01 | 2002-11-26 | Cool Options, Inc. | Thermally conductive electronic device case |
-
2011
- 2011-12-12 US US13/316,622 patent/US20120157600A1/en not_active Abandoned
- 2011-12-20 WO PCT/US2011/066333 patent/WO2012088207A2/en active Application Filing
- 2011-12-20 JP JP2013546353A patent/JP2014503658A/en not_active Withdrawn
- 2011-12-20 CN CN201180061463.3A patent/CN103270099B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040251804A1 (en) * | 2003-06-11 | 2004-12-16 | Cool Options, Inc. | Thermally-conductive plastic articles having light reflecting surfaces |
| CN101861353A (en) * | 2007-11-16 | 2010-10-13 | 纳幕尔杜邦公司 | Thermally conductive resin compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012088207A3 (en) | 2012-09-20 |
| JP2014503658A (en) | 2014-02-13 |
| WO2012088207A2 (en) | 2012-06-28 |
| CN103270099A (en) | 2013-08-28 |
| US20120157600A1 (en) | 2012-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103270099B (en) | Molded thermoplastic articles comprising thermally conductive polymers | |
| TWI502025B (en) | Stain-resistant article and use thereof | |
| JP6346181B2 (en) | Semi-aromatic polyamide resin composition and molded article containing the same | |
| CN101006136B (en) | Aromatic polyamide composition and article manufactured therefrom | |
| JP2013500351A (en) | Thermally conductive thermoplastic resin composition and related applications | |
| JP7085294B2 (en) | Polyamide composition dyed black, its manufacture and use | |
| CN102482450B (en) | Thermally conductive polymer compositions and articles made therefrom | |
| CN102159639A (en) | Resin composition | |
| CN102115590B (en) | Polyamide resin composition with good reflectance, impact strength, heat resistance, and water resistance and method of preparing the same | |
| US11958973B2 (en) | Resin composition, kit, method for manufacturing resin composition, method for manufacturing formed article, and formed article | |
| CN102115592A (en) | Polyamide based resin composition having excellent whiteness, thermal conductivity, and extruding moldability, and preparation method and product thereof | |
| KR101933749B1 (en) | Resin composition for reflective plate and reflective plate | |
| CN103119092A (en) | Thermally conductive resin composition | |
| JP2020012093A (en) | Polyamide resin composition, kit, method for producing molding and molding | |
| CN103492488A (en) | Flame-retardant molding materials | |
| WO2024004933A1 (en) | Polyamide resin composition for reflective plate, and reflective plate | |
| JP2021172783A (en) | Molding method and reflective material | |
| WO2024104965A1 (en) | Mixed metal-oxide compositions as stabilizer for flame retardant polyamides | |
| JP2021155616A (en) | Resin composition for reflective material and reflective material | |
| JP2001214052A (en) | Thermoplastic resin composition and its use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150311 Termination date: 20151220 |
|
| EXPY | Termination of patent right or utility model |